Combinations Containing PVA And Certain Herbicides With Improved Properties

ABSTRACT

The present invention relates to the technical field of crop protection. More specifically, the invention relates to combinations of (I) polyvinyl alcohol (PVA) and (II) a composition comprising one or more water soluble herbicidal active ingredients and certain further constituents, said combination having improved properties, in particular regarding rainfastness and/or herbicidal efficacy. The invention also relates to the use of such combinations.

The present invention relates to the technical field of crop protection.More specifically, the invention relates to combinations of (I)polyvinyl alcohol (PVA) and (II) a composition comprising one or morewater soluble herbicidal active ingredients and certain furtherconstituents, said combination having improved properties, in particularregarding rainfastness and/or herbicidal efficacy. The invention alsorelates to the use of such combinations.

Crop protectant compositions can be formulated in many different ways,with the possibility of the characteristics of the active ingredientsand the nature of the formulation giving rise to problems in terms ofstability, efficacy, and applicability of the formulations. Moreover,certain formulations are more advantageous on economic and environmentalgrounds than others.

Water-based formulations generally have the advantage that they requirea low fraction of organic solvents, or none at all. On the other hand,the distribution of the constituents in such formulations is ofteninadequate unless appropriate combinations of auxiliaries are used. Theperformance properties of such formulations frequently depend on a largenumber of variable parameters, making it impossible simply to selectcomponents of known systems and to combine them with the activeingredients intended for new formulation, if the resultant formulationis to be biologically active, stable on storage, and ideal from theapplications standpoint.

Rainfastness is the ability of a pesticide (pesticide formulation) towithstand rainfall and retain biological efficacy to a higher degree.For most pesticides, rain immediately after an application will removemost of the pesticide residues from the leave surface. A productremaining to a higher portion on the leave surfaces after a rain eventallows for more of the pesticide to penetrate into the leave andproviding weed control activity.

A pesticide is considered “rainfast” after application if it hasadequately dried, physically retained on the leave surface or has beenabsorbed by plant tissues so that it remains effective after rainfall orirrigation.

The degree of rainfastness depends on many factors. The most importantis the rain. All pesticide products need a certain amount of drying timebetween application and rainfall.

Some pesticide products are designed with adjuvants, materials added tothe formulation to increase the effectiveness. Some adjuvants improverainfastness by enhancing the capacity of the active ingredient topenetrate into the leave or to bind to the plant/leave surface and arestill sufficient selective in herbicide tolerant crops.

Post-emergent herbicides are applied on weeds that have already emerged,one example is glyphosate. Traditional formulations of glyphosaterequired a dry period of 6 to 12 hours after application. Rain orirrigation within that period would reduce effectiveness and require asecond application.

Standard formulations, therefore, are rarely suitable for meetingparticular requirements, and it is necessary involve a great deal ofexperimental work to develop an appropriate formulation. Many herbicidalformulations containing water-soluble active crop protectant ingredientshave been described.

Examples of herbicidal formulations comprising glufosinate and certainsurfactants are known from U.S. Pat. No. 4,400,196.

U.S. Pat. No. 5,152,823 discloses aqueous pesticidal agents based onactive substance-containing dispersions in combination withwater-soluble active substances and contain alkyl ether sulfatescombined with ethoxylated fatty alcohols and sulfosuccinic monoesters assurfactants.

U.S. Pat. No. 5,258,358 mentions liquid herbicidal compositionscomprising glufosinate-ammonium and an alkyl polyglycoside, optionallyin combination with certain other surfactants.

U.S. Pat. No. 5,332,714 relates to low-foam concentrated liquid aqueouspreparations of plant protecting agents which contain sulfato- orsulfonato-containing surfactants as wetting agents and certain othersurfactants as defoamers.

WO 92/12637 discloses improved dry and water soluble glyphosateformulations.

U.S. Pat. No. 6,713,433 teaches liquid concentrate herbicidal emulsioncompositions comprising a water-soluble herbicide, an oil-solubleherbicide, a stabilizing amount of water-soluble chlorides, and one ormore surfactants.

US 2005/0266999 and U.S. Pat. No. 8,110,529 relate to concentratedaqueous preparations for crop protection comprising certain types ofsurfactants and ammonium salts or aluminum silicates.

WO 2007/092351 discloses stable, concentrated compositions comprising awater-soluble herbicidal ingredient, an alkyl ether sulfate, an organicsolvent and an alkyl polyglucoside.

U.S. Pat. No. 8,901,041 discloses low-foam aqueous formulations for cropprotection containing anionic surfactants and specific silicone-baseddefoamers.

WO 2004/105916 relates to aqueous concentrate composition comprising anagrochemical, one or more foam-inducing surfactants and an antifoamagent wherein the antifoam agent is incorporated into the composition asa solution in an organic solvent.

ACS Appl. Mater. Interfaces 2016, 8, 14220-14230 investigated therainfastness of poly(vinyl alcohol) deposits on Vicia faba leafsurfaces.

U.S. Pat. No. 2,510,839 discloses improved compositions comprising2,4-D, petroleum oils with a specific viscosity and differentsulfonates.

U.S. Pat. No. 4,954,497 relates to certain acrylic acid morpholidesshowing excellent fungicidal effects even after the rainfall afterspraying, superior to those of known compounds.

WO 95/16351 and WO 97/00010 relate to surfactants providing enhancedefficacy and/or rainfastness to pesticide formulations.

U.S. Pat. No. 9,374,996 provides a pesticide composition comprising acopolymer of acrylic acid, poly(alkylene glycol) (meth)acrylate, andalkyl (meth)acrylate with high rainfastness and/or retention of thepesticide.

U.S. Pat. No. 5,491,125 teaches liquid herbicidal compositionscomprising glufosinate in combination with certain types of surfactantsand a low content of organic solvents which possess improved herbicidalactivities, high low-temperature stability and rain resistance.

In view of these known formulations, the object of the present inventionwas to provide combinations with one or more water-soluble activeherbicidal ingredients having improved properties, in particularimproved rainfastness and/or herbicidal properties.

It was found that combinations of polyvinyl alcohol and compositions ofwater-soluble active herbicidal ingredients containing certainsurfactants have such improved properties, in particular improvedrainfastness and/or herbicidal properties, wherein said combinationspreferably additionally comprise certain esters.

The invention therefore primarily relates to combinations comprising orconsisting of

(I) one or more polyvinyl alcohols,

(II) a composition comprising or consisting of

(a) one or more water-soluble herbicidal active crop protectantingredients (type (a) active ingredients),

(b) one or more C₆-C₁₆ fatty alcohol polyethylene glycol ether sulfatesand/or C₆-C₁₆ alkylpolyglycosides, and/or C₁₀-C₁₈ fatty alkyl amineethoxylates,

wherein the ratio of the total amount of constituent (I) to the totalamount of constituent (II) is in the range of from 1:100 to 1:5, basedon the total weight of the combination.

It has been found that the combinations according to the presentinvention exhibit improved properties, in particular improvedrainfastness and/or herbicidal properties, due to the combination ofconstituents (I) and (II) as defined in the context of the presentinvention.

In such a combination, the preferred ratio of the total amount by weightof polyvinyl alcohols of constituent (I) to constituent (II), i.e. acomposition as defined to be used according to the present invention, isin the range of from 1:100 to 1:5, preferably in the range of from 1:50to 1:10, more preferably in the range of from 1:40 to 1:10, even morepreferably in the range of from 1:30 to 1:12, in each case based on thetotal weight of the combination.

Such a combination can be in form of a kit-of-parts, a co-pack (suitableor recommended for tank-mixing) or a tank-mix. A co-pack in the contextof the present invention preferably is a twin-pack or a tri-pack.

In the context of the present invention the polyvinyl alcohols used asconstituent (I) with constituent (II) in a combination according of thepresent invention preferably are partially hydrolyzed polyvinyl acetateswith a degree of hydrolysis in the range of from 75 to 97 mol.-%, morepreferably with a degree of hydrolysis in the range of from 80 to 95mol.-%, and even more preferably with a degree of hydrolysis in therange of from 84 to 92 mol.-%.

The degree of polymerization of the polyvinyl alcohols used asconstituent (I) preferably is in the range of 150 to 1000, morepreferably in the range of 250 to 750, and even more preferably in therange of 250 to 500.

The viscosity of a 4 wt.-% aqueous solution of the polyvinyl alcoholsused as constituent (I) [measured at 20° C. according to DIN53015:2001-02 (issued 2001-02) (Measurement of viscosity by means of therolling ball viscometer] preferably is in the range of 3 to 50 mPas,more preferably is in the range of 3.5 to 10 mPas and even morepreferably is in the range of 3.5 to 6 mPas.

Such polyvinyl alcohols are commercially available, for example thePOVAL® product range from Kuraray.

Generally and preferably, the compositions used as constituent (II) inthe context of the present invention are liquid at 25° C. and 1013 mbar.

The water-soluble herbicidal active crop protectant ingredients ofconstituent (a) of the compositions used as constituent (II) in thecontext of the present invention and the other herbicidal active cropprotectant ingredients and herbicide safeners of the optionalconstituent (h) of combinations of the present invention, preferably ofthe compositions used as constituent (II) in the context of the presentinvention, and the common names used herein are commonly known; see, forexample, “The Pesticide Manual” 16th Edition, British Crop ProtectionCouncil 2012; these include the known stereoisomers (in particularracemic and enantiomeric pure isomers) and derivatives such as salts oresters, and particularly the commercially customary forms.

In the context of the present invention water-soluble herbicidal activecrop protectant ingredients (type (a) active ingredients) have a watersolubility at 20° C. and 1013 mbar (typically at a pH in the range of4-7, depending on the form) of at least 5 g/l or higher, preferably ofat least 10 g/l or higher, more preferably of at least 20 g/l or higher.

To allow a high concentration of one or more water-soluble herbicidalactive crop protectant ingredients (type (a) active ingredients) in thecompositions used as constituent (II) in the context of the presentinvention are preferably used in form of their salts since thesegenerally speaking show higher water solubility.

The compositions used as constituent (II) in the context of the presentinvention preferably comprise as constituent (a) one or morewater-soluble active crop protectant ingredients selected from the groupconsisting of glufosinate[2-amino-4-[hydroxy(methyl)phosphinoyl]butanoic acid] and salts thereof,glyphosate [N-(phosphonomethyl)glycine] and salts thereof, MCPA[(4-chloro-2-methylphenoxy)acetic acid] and salts thereof, dicamba[3,6-dichloro-2-methoxybenzoic acid] and salts thereof, 2,4-D[2,4-dichlorophenoxy)acetic acid] and salts thereof and dichlorprop[2-(2,4-dichlorophenoxy)propanoic acid] and the salts thereof.

The compositions used as constituent (II) in the context of the presentinvention preferably comprise as constituent (a) one or morewater-soluble active crop protectant ingredients selected from the groupconsisting of glufosinate-ammonium, glufosinate-sodium,L-glufosinate-ammonium, L-glufosinate-sodium, glyphosate-diammonium,glyphosate-dimethylammonium, glyphosate-isopropylammonium,glyphosate-monoammonium, glyphosate-potassium, glyphosate-dipotassium,glyphosate-sesquisodium (N-(phosphonomethyl)glycine sodium salt (2:3)),glyphosate-trimesium, MCPA-dimethylammonium, MCPA-diolamine,MCPA-olamine, MCPA-potassium, MCPA-sodium, MCPA-trolamine,dicamba-biproamine, dicamba-diglycolamine, dicamba-dimethylammonium,dicamba-diolamine, dicamba-isopropylammonium, dicamba-olamine,dicamba-potassium, dicamba-sodium, dicamba-trolamine, dicamba-choline,dicamba-BAPMA (N,N-bis-(3-aminopropyl)methylamine salt), 2,4-D-ammonium,2,4-D-choline, 2,4-D-BAPMA (N,N-bis-(3-aminopropyl)methylamine salt),2,4-D-diethylammonium, 2,4-D-dimethylammonium, 2,4-D-diolamine,2,4-D-dodecylammonium, 2,4-D-heptylammonium, 2,4-D-isopropylammonium,2,4-D-lithium, 2,4-D-potassium, 2,4-D-sodium, 2,4-D-tetradecylammonium,2,4-D-triethylammonium, 2,4-D-tris(2-hydroxypropyl)ammonium,2,4-D-trolamine, dichlorprop-dimethylammonium,dichlorprop-ethylammonium, dichlorprop-potassium, anddichlorprop-sodium.

Particularly preferably, constituent (a) of compositions used asconstituent (II) in the context of the present invention comprises orconsists of glufosinate-ammonium, glufosinate-sodium,L-glufosinate-ammonium, L-glufosinate-sodium, glyphosate-potassium,glyphosate-ammonium, glyphosate-dimethylammonium,glyphosate-isopropylammonium, glyphosate-trimesium (sulfosate),dicamba-diglycolamine, dicamba-BAPMA, and 2,4-D-choline.

Constituent (b) of the compositions used as constituent (II) in thecontext of the present invention is a group of surfactants known fromthe prior art to allow good stability and/or activity of compositionscomprising water-soluble herbicidal active crop protectant ingredients(type (a) active ingredients).

The C₆-C₁₆ fatty alcohol polyethylene glycol ether sulfates ofconstituent (b) of the compositions used as constituent (II) in thecontext of the present invention preferably correspond to the formulaCH₃(CH₂)_(m)(OCH₂CH₂)_(n)OSO₃M, wherein M is a cation, m denotes aninteger of from 4 to 15 and n is 2, 3, 4 or 5.

Preferably, M is selected from Na⁺, K⁺ or NH₄ ⁺, m denotes an integer offrom 6 to 15 and n is 2, 3, 4 or 5.

More preferably, M is selected from Na⁺, K⁺ or NH₄ ⁺, m denotes aninteger of from 9 to 15 and n is 2, 3, 4 or 5.

More preferred fatty alcohol polyethylene glycol ether sulfates asconstituent (b) are C₁₀-C₁₆ fatty alcohol diethylene glycol ethersulfates (i.e. n is 2).

The C₆-C₁₆ alkylpolyglycosides of constituent (b) as defined in thecompositions used as constituent (II) in the context of the presentinventions preferably are C₆-C₁₆ alkylpolyglucosides, more preferablyC₈-C₁₂ alkylpolyglucosides.

C₆-C₁₆ Alkylpolyglycosides, in particular C₆-C₁₆ alkylpolyglucosides,suitable as constituent (b) are known in the art and commerciallyavailable, e.g. alkylpolysaccharides and mixtures thereof such as those,for example, from the ®Atplus series (Croda) with or without addition ofinorganic salts such as ammonium sulfate, alkylpolyglycosides in theform of the Agnique PG® grades from BASF, an example being ®Agnique PG8107 (fatty alcohol C₈-C₁₀ glucosides), ®Agnique PG 9116 (fatty alcoholC₉-C₁₁ glucosides), alkylpolyglycoside/alkylpolysaccharide mixturesbased on C₈-C₁₀ fatty alcohol such as ®Glucopon 225 DK and ®Glucopon 215CSUP (BASF).

The C₁₀-C₁₈ fatty alkyl amine ethoxylates of constituent (b) ofcompositions used as constituent (II) in the context of the presentinvention preferably correspond to the formulaH(OCH₂CH₂)_(p)N(R⁶)(CH₂CH₂O)_(q)H, wherein R⁶ denotes a C₁₀-C₁₈ alkylgroup, p denotes an integer of from 1 to 10 and q denotes an integer offrom 1 to 10.

Preferably, R⁶ denotes a C₁₂-C₁₈ alkyl group, p denotes an integer offrom 1 to 8 and q denotes an integer of from 1 to 8.

More preferably, R⁶ denotes a C₁₂-C₁₆ alkyl group, p denotes an integerof from 1 to 6 and q denotes an integer of from 1 to 6.

More preferably, constituent (b) of compositions used as constituent(II) in the context of the present invention comprises or consists ofone or more C₁₀-C₁₆ fatty alcohol diethylene glycol ether sulfate saltsand/or C₈-C₁₂ alkylpolyglucosides with a degree of polymerization ofless than 5, and/or C₁₂-C₁₆ alkyl amine ethoxylates with 2 to 10ethylene oxide (EO) units.

Particularly preferably, constituent (b) of compositions used asconstituent (II) in the context of the present invention comprises orconsists of one or more C₁₂-C₁₄ fatty alcohol diethylene glycol ethersulfate sodium-, potassium-, ammonium-salts (preferably sodium salts)and/or C₈-C₁₀ alkylpolyglucosides with a degree of polymerization ofless than 2, and/or C₁₂-C₁₄ alkyl amine ethoxylates with 4 to 8 ethyleneoxide (EO) units [preferably 3-isotridecyloxypropanamine, ethoxylated(CAS number 68478-96-6; systematic name:Poly(oxy-1,2-ethanediyl),.alpha.,.alpha.′-[[[3-(tridecyloxy)propyl]imino] di-2,1-ethanediyl]bis[.omega.-hydroxy-, branched)].

In a composition used as constituent (II) in the context of the presentinvention wherein glufosinate-ammonium is (part of) constituent (a), thepreferred constituent (b) comprises or consists of one or more C₁₀-C₁₆fatty alcohol diethylene glycol ether sulfate salts and/or C₈-C₁₂alkylpolyglucosides as defined above, preferably as defined as one ofthe preferred or more preferred embodiments.

In a composition used as constituent (II) in the context of the presentinvention wherein one of the above-mentioned glyphosate-salts is (partof) constituent (a), the preferred constituent (b) comprises or consistsof one C₈-C₁₂ alkylpolyglucosides and/or C₁₂-C₁₆ alkyl amine ethoxylateswith 2 to 10 ethylene oxide (EO) units as defined above, preferably asdefined as one of the preferred or more preferred embodiments.

The advantage of the C₆-C₁₆ fatty alcohol polyethylene glycol ethersulfates as (part of) constituent (b) of the present invention is thatthe amount of constituent (c) that is achievable to be incorporated intoa composition according to the present invention is higher, thusallowing further improved rainfastness and/or herbicidal activity ofsaid composition.

Preferably, the combination according to the present invention orconstituent (II) comprises one or more further constituents selectedfrom the group consisting of constituents (c) to (h):

(c) one or more esters selected from the group consisting of (c1) to(c3):

(c1) R¹COOR², wherein R¹ denotes a C₅-C₁₃ alkyl group and R² denotes aC₆-C₁₄ alkyl group, wherein the total number of carbon atoms in R¹ andR² taken together is an integer in the range of from 14 to 22,

(c2) R³OOC—(CH₂)x-COOR⁴, wherein R³ and R⁴, independent of each other,denote a C₄-C₁₂ alkyl group, and x is an integer in the range of from 1to 6,

(c3) (R⁵O)₃P═O, wherein R⁵, independent of each other, denote a C₄-C₁₆alkyl group, wherein the total number of carbon atoms in the three R⁵taken together is an integer in the range of from 18 to 42,

(d) organic solvents,

(e) water,

(f) other surfactants,

(g) other formulation adjuvants,

(h) one or more other herbicidal active crop protectant ingredientsand/or herbicide safeners.

The (preferred) constituents (c) to (h) optionally present in acombination according to the present invention are the same as the(preferred) constituents (c) to (h) described in detail hereinafter forcompositions used as constituent (II) in the context of the presentinvention. Preferably, constituents (d) to (h) are part of compositionsused as constituent (II) in the context of the present invention, and ina preferred embodiment, constituents (c) to (h) are part of compositionsused as constituent (II) in the context of the present invention.

Constituent (c), preferably as part of compositions used as constituent(II) in the context of the present invention, is a group of estersdefined by constituents (c1), (c2) and (c3) having the followingstructures.

Constituent (c1) in the context of the present invention has thefollowing structure:

wherein R¹ and R² each denote the respective group defined herein.

Constituent (c2) in the context of the present invention has thefollowing structure:

wherein R³, R⁴ and x each have the respective meaning defined herein.

Constituent (c3) in the context of the present invention has thefollowing structure:

wherein each R⁵ denotes the respective group defined herein.

The esters used as constituent (c), preferably as part of compositionsused as constituent (II) in the context of the present invention, can beproduced by any method known in the art, for example esterification ofthe respective acid or acid halide moiety and the respective alcoholR²OH, R³OH, R⁴OH, or R⁵OH. Many esters of constituent (c) of thecompositions according to the present are commercially available.

Preferred alkyl groups in the context of the constituents (c1), (c2) and(c3) of constituent (c), preferably as part of compositions used asconstituent (II) in the context of the present invention, i.e. R¹, R²,R³, R⁴, and R⁵ respectively, are linear and branched alkyl groups, andpreferably are selected from the group consisting of 1-butyl, 2-butyl,isobutyl, tert-butyl, 1-pentyl, 2-pentyl, isopentyl, 1-hexyl, 2-hexyl,isohexyl, 1-heptyl, 2-heptyl, isoheptyl, 1-octyl, 2-octyl, isooctyl,2-ethylhexyl, 3,5,5-trimethylhexyl, 3,4,4-trimethylpentyl, 1-nonyl,2-nonyl, isononyl, 1-decyl, 2-decyl, isodecyl, 2-propylheptyl,1-dodecyl, 2-dodecyl, and isododecyl. More preferred alkyl groups R¹,R², R³, R⁴, and R⁵ in the context of the constituents (c1), (c2) and(c3) according to the present invention are branched alkyl groups, eachpreferably selected from the group consisting of 2-hexyl, isohexyl,2-heptyl, isoheptyl, 2-octyl, isooctyl, 2-ethylhexyl,3,5,5-trimethylhexyl, 3,4,4-trimethylpentyl, 2-nonyl, isononyl, 2-decyl,isodecyl, 2-dodecyl, and isododecyl.

Preferably, constituent (c), preferably as part of compositions used asconstituent (II) in the context of the present invention, comprises orconsists of one or more esters selected from the group consisting of(c1) to (c3):

-   (c1) R¹COOR², wherein R¹ denotes a C₇-C₉ alkyl group and R² denotes    a C₈-C₁₀ alkyl group, wherein the total number of carbon atoms in R¹    and R² taken together is an integer in the range of from 16 to 20,-   (c2) R³OOC—(CH₂)x-COOR⁴, wherein R³ and R⁴, independent of each    other, denote a C₆-C₁₀ alkyl group, and x is an integer in the range    of from 2 to 5,-   (c3) (R⁵O)₃P═O, wherein R⁵, independent of each other, denote a    C₆-C₁₂ alkyl group.

More preferably, constituent (c), preferably as part of compositionsused as constituent (II) in the context of the present invention,comprises or consists of one or more esters selected from the groupconsisting of (c1) to (c3):

-   (c1) R¹COOR², wherein R¹ denotes a branched C₇-C₉ alkyl group and R²    denotes a branched C₈-C₁₀ alkyl group, wherein the total number of    carbon atoms in R¹ and R² taken together is an integer in the range    of from 16 to 20,-   (c2) R³OOC—(CH₂)x-COOR⁴, wherein R³ and R⁴, independent of each    other, denote a branched C₆-C₁₀ alkyl group, preferably each a    2-ethylhexyl group, and x is an integer in the range of from 2 to 5,-   (c3) (R⁵O)₃P═O, wherein R⁵, independent of each other, denote a    branched C₆-C₁₂ alkyl group.

Even more preferably, constituent (c), preferably as part ofcompositions used as constituent (II) in the context of the presentinvention, comprises or consists of one or more esters selected from thegroup consisting of (c1) to (c3):

-   (c1) R¹COOR², wherein R¹ denotes a branched C₈ alkyl group and R²    denotes a branched C₉ alkyl group,-   (c2) R³OOC—(CH₂)x-COOR⁴, wherein R³ and R⁴, independent of each    other, denote a branched C₈ alkyl group, preferably each a    2-ethylhexyl group, and x is 2, 3 or 4,-   (c3) (R⁵O)₃P═O, wherein R⁵, independent of each other, denote a    branched C₈ alkyl group.

Preferably, from a practical perspective and for reasons of (syntheticand/or commercial) availability, in compositions used as constituent(II) in the context of the present invention, in constituent (c2)preferably R³ and R⁴ both denote the same alkyl group, and inconstituent (c3) all three R⁵ denote the same alkyl group.

In own experiments the following constituents (c) gave particularlyimproved properties for the compositions used as constituent (II) in thecontext of the present invention. Therefore, preferably constituent (c),preferably as part of compositions used as constituent (II) in thecontext of the present invention, comprises or consists of one or moreesters selected from the group consisting of

(c1) 3,5,5-trimethylhexyl 3,5,5-trimethylhexanoate-methyloctyl7-methyloctanoate,

(c2) bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) succinate, and

(c3) tris(2-ethylhexyl) phosphate.

It was for example found that in case of glyphosate salts as constituent(a), the improved properties mentioned above of the compositions used asconstituent (II) in the context of the present invention were observedwhen constituent (c) comprised or consisted of constituent (c2). Forexample, particularly improved rainfastness was observed whenbis(2-ethylhexyl) adipate was used as constituent (c2).

It was for example also found that in case of glufosinate salts asconstituent (a), the improved properties mentioned above of compositionsused as constituent (II) in the context of the present invention wereobserved when constituent (c) comprised or consisted of constituents(c1) or (c3). For example, particularly improved rainfastness wasobserved when isononyl isononanoate and/or 3,5,5-trimethylhexyl3,5,5-trimethylhexanoate was used as constituent (c1) or whentris(2-ethylhexyl) phosphate was used as constituent (c3).

Preferred according to the present invention are compositions used asconstituent (II) in the context of the present invention, wherein theratio by weight of the total amount of constituent (a) to the totalamount of constituent (b) is in the range of from 10:1 to 1:6, andpreferably is in the range of from 8:1 to 1:3.

Preferably, in the combination according to the present invention or incompositions used as constituent (II) in the context of the presentinvention the ratio by weight of the total amount of constituent (a) tothe total amount of constituent (c) is in the range of from 60:1 to 2:1,and preferably is in the range of from 40:1 to 3:1.

Preferred are combinations according to the present invention, whereinin the combination comprises the ratio of the total amount by weight ofpolyvinyl alcohols of constituent (I) to the total amount of constituent(c) is in the range of from 5:1 to 1:5, preferably in the range of from3:1 to 1:3, more preferably in the range of from 2:1 to 1:2, in eachcase based on the total weight of the combination.

The optimum ratio ranges of constituent (a) to constituents (b) and (c)in a composition used as constituent (II) in the context of the presentinvention depend to some extent on the water-soluble herbicidal activecrop protectant ingredient used and on the amount thereof included inthe composition.

For example, in a composition used as constituent (II) in the context ofthe present invention wherein glufosinate-ammonium is (part of)constituent (a), the preferred ratio by weight of the total amount ofconstituent (a)

to the total amount of constituent (b) is in the range of from 3:2 to1:6,

and/or

to the total amount of constituent (c) is in the range of from 25:1 to2:1.

More preferably, in a composition used as constituent (II) in thecontext of the present invention wherein glufosinate-ammonium is (partof) constituent (a), the ratio by weight of the total amount ofconstituent (a)

to the total amount of constituent (b) is in the range of from 1:1 to1:3, and/or

to the total amount of constituent (c) is in the range of from 10:1 to3:1.

For example, in a composition used as constituent (II) in the context ofthe present invention wherein one of the above-mentionedglyphosate-salts is (part of) constituent (a), the preferred ratio byweight of the total amount of constituent (a)

to the total amount of constituent (b) is in the range of from 8:1 to1:1,

and/or

to the total amount of constituent (c) is in the range of from 25:1 to4:1.

More preferably, in a composition used as constituent (II) in thecontext of the present invention wherein one of the above-mentionedglyphosate-salts is (part of) constituent (a), the ratio by weight ofthe total amount of constituent (a)

to the total amount of constituent (b) is in the range of from 7:1 to2:1,

and/or

to the total amount of constituent (c) is in the range of from 20:1 to5:1.

In a preferred embodiment, the combination according to the presentinvention is a tank-mix obtainable or obtained by mixing a combinationas defined herein, preferably in one of the preferred embodiments, andwater as constituent (III), wherein the ratio by weight of the totalamount of constituent (III) to the total amount of the combination asdefined herein, preferably as defined in one of the preferredembodiments, in the tank-mix is in the range of from 1000:1 to 10:1,preferably in the range of from 500:1 to 25:1, more preferably in therange of from 400:1 to 50:1.

Suitable organic solvents of constituent (d) of compositions used asconstituent (II) in the context of the present invention are differentfrom constituent (c) and preferably are water-miscible organic solvents,examples being

aliphatic alcohols, such as lower alkanols, for example, such asmethanol and ethanol or polyhydric alcohols such as ethylene glycol andglycerol,

polar ethers such as alkylene glycol monoalkyl and dialkyl ethers, suchas propylene glycol, propylene glycol monomethyl ether, propylene glycolmonoethyl ether, dipropylene glycol, dipropylene glycol monomethylether, ethylene glycol monomethyl ether or monoethyl ether, diethyleneglycol, hexylene glycol, diglyme and tetraglyme;

amides such as dimethylformamide, dimethylacetamide,dimethylcaprylamide, dimethylcapramide and N-alkylpyrrolidones.

Preference is given here to largely water-miscible organic solvents.Preferably, constituent (d) comprises or consists of propylene glycolmonomethyl ether, dipropylene glycol and/or propylene glycol, andpreferably comprises or consists of 1-methoxy-2-propanol and/ordipropylene glycol.

Preferably, a composition used as constituent (II) in the context of thepresent invention contains constituent (d) in a total amount 0% to 15%by weight, based on the total weight of the composition. The totalamount of constituent (d) in a composition used as constituent (II) inthe context of the present invention however inter alia depends on thewater-soluble herbicidal active crop protectant ingredient(s) present as(part of) constituent (a), i.e. the type (a) active ingredients.

For example, in a composition used as constituent (II) in the context ofthe present invention wherein glufosinate-ammonium is (part of)constituent (a), the preferred total amount by weight of constituent (d)is in the range of 5% to 15% by weight, preferably in the range of 7% to12% by weight, in each case based on the total weight of thecomposition. These amounts in particular apply for the case thatglufosinate-ammonium is (part of) constituent (a) and constituent (d)comprises or consists of propylene glycol monomethyl ether, dipropyleneglycol and/or propylene glycol, and preferably comprises or consists of1-methoxy-2-propanol and/or dipropylene glycol.

For example, in a composition used as constituent (II) in the context ofthe present invention wherein a glyphosate-salt is (part of) constituent(a), the preferred total amount by weight of constituent (d) is in therange of 0% to 5% by weight, preferably 0% by weight (i.e. free oforganic solvents of constituent (d)), in each case based on the totalweight of the composition.

The organic solvents of constituent (d) of the compositions used asconstituent (II) in the context of the present invention should only tobe used in amounts such that the aqueous phase is stable, preferably inthe form of a thermodynamically stable aqueous solution.

The compositions used as constituent (II) in the context of the presentinvention may optionally comprise as constituent (f) other surfactants(anionic, cationic or zwitterionic and/or nonionic surface-activecompounds (surfactants)) not belonging the group of constituent (b) ofthe compositions used as constituent (II) in the context of the presentinvention which are able to further contribute to improved stability,further improved plant availability or further improved activity of thewater-soluble herbicidal active crop protectant ingredients (type (a)active ingredients).

As constituent (g), the compositions used as constituent (II) in thecontext of the present invention can comprise customary formulationadjuvants, examples being inert materials, such as stickers, wetters,dispersants, emulsifiers, penetrants, preservatives, inorganic salts,stabilizers, frost protectants, fillers, carriers and colorants,evaporation inhibitors and pH modifiers (buffers, acids, and bases),viscosity modifiers (e.g., thickeners) or defoamers. The addition ofinorganic salts, preferably ammonium salts such as ammonium chloride orammonium sulfate, may be of advantage, particularly in combination withcertain surfactants or with polyvinyl alcohol (see hereinafter).

Due to the presence of constituent (b), it is often advantageous toinclude a defoamer as (part of) constituent (g) of the presentinvention. Suitable defoamers include all customary defoamers,preferably silicone-based defoamers, such as silicone oils, for example.The silicone oils can also be used as emulsions.

Defoamers from the group of the linear polydimethylsiloxanes contain astheir chemical backbone a compound of the formulaHO—[Si(CH₃)₂—O-]_(n)—H, in which the end groups are modified, byetherification for example, or in general are attached to the groups—Si(CH₃)₃. Preferred defoamers are those from the group of the linearpolydimethylsiloxanes, preferably containing silica, in particular thosementioned in U.S. Pat. No. 8,901,041. Silica embracesforms/modifications such as polysilicic acids, meta-silicic acid,ortho-silicic acid, silica gel, silicic acid gels, kieselguhr,precipitated SiO₂, etc.

Preferred according to the present invention are compositions used asconstituent (II) in the context of the present invention, whereinconstituent (d) comprises or consists of propylene glycol monomethylether, dipropylene glycol and/or propylene glycol, and preferablycomprises 1-methoxy-2-propanol,

and/or

constituent (f) comprises or consists of alkyl sulfosuccinate salts(diesters and monoesters), preferably comprises or consists of C₆-C₁₄alkyl sulfosuccinate monoester salts, more preferably comprises orconsists of laureth-3 sulfosuccinate salts, in particular disodiumlaureth-3 sulfosuccinate,

and/or

constituent (g) comprises a defoaming agent, preferably anpolydimethylsiloxane oil with silica gel.

Preferred according to the present invention are compositions used asconstituent (II) in the context of the present invention, whereinconstituent (d) comprises 1-methoxy-2-propanol, and wherein thecomposition preferably comprises polydimethylsiloxane oil with silicagel as defoaming agent (as (part of) constituent (g)),

and

constituent (f) comprises or consists of alkyl sulfosuccinate salts(diesters and monoesters), preferably comprises or consists of C₆-C₁₄alkyl sulfosuccinate monoester salts, more preferably comprises orconsists of laureth-3 sulfosuccinate salts, in particular disodiumlaureth-3 sulfosuccinate.

As constituent (h), the compositions used as constituent (II) in thecontext of the present invention can comprise other herbicidal activecrop protectant ingredients (i.e. different from constituent (a)) and/orherbicide safeners. Preferably, such other herbicidal active cropprotectant ingredients are have a low water solubility at 20° C. and1013 mbar, preferably at pH 7, of 1 g/l or lower, more preferably of 0.5g/l or lower. Preferred herbicide safeners of constituent (h) arecyprosulfamide, isoxadifen-ethyl, mefenpyr-diethyl, benoxacor, flurazoland cloquintozet-mexyl.

In case the compositions used as constituent (II) in the context of thepresent invention comprise other herbicidal active crop protectantingredients (i.e. different from constituent (a)) having a low watersolubility as constituent (h), it is preferred to include one or morestabilizers as part of constituent (f) or (g).

Such a stabilizer can be a dispersant or a suspending agent, e. g. fromthe group of ionic polymers, like Sodium naphthalene sulphonateformaldehyde condensates or Kraft-lignosulfonate sodium salt, likeMorwet D245 (Akzo Nobel) or Kraftsperse 25M (Ingevity), or from thegroup of non-ionic polymers, like Polyethoxylated polymethacrylates,like Atlox 4913 (Croda).

Such a stabilizer can be a dispersant or suspending agent, e. g, fom thegroup of ionic surfactants, like Dialkyl naphthalene sulfate sodium,like Oparyl MT800 (Bozetto), or non-ionic surfactants, like Tristyrylphenol alkoxylates, like Soprophor 796/P (Solvay) or block-co-polymersof ethylene/propylene oxides, like Pluronic PE 6800 (BASF).

Such a stabilizer can be from the group of the aluminum silicates andcan be a mineral fiber, such as a fiberlike magnesium and aluminumsilicate attapulgite, preferably ®Attagel 40 (BASF) or ®Clarsol ATC(from CECA, Dusseldorf, Germany) Also suitable are ®Bentone EW (fromElementis), which likewise comprise hectorites as their base material.

The constituents used to prepare and obtain the compositions used asconstituent (II) in the context of the present invention are known andmany of these constituents are commercially available.

The compositions used as constituent (II) in the context of the presentinvention are prepared by conventional methods, by mixing andhomogenizing the active ingredient (a) in solid or already dissolvedform, and all other constituents, with stirring where appropriate.

In a further aspect, the present invention relates to a process forpreparing a combination according to the present invention as definedherein, which comprises mixing constituents (I) to (II), and preferablywater as constituent (III), and optionally further constituents of saidcombination mentioned in the context of the present invention.

In case constituents (f), (g) and/or (h) as defined herein are presentin a composition used as constituent (II) in the context of the presentinvention, and e.g. are poorly water soluble, it may be beneficial toinclude a milling step, e.g. using a colloid mill or stirred bead mill.

The compositions used as constituent (II) in the context of the presentinvention preferably exhibit good storage properties (i.e. storagestability, including low-temperature stability), high bioavailabilityand hence activity of the water-soluble active crop protectantingredients, i.e. of constituent(s) (a).

The compositions used as constituent (II) in the context of the presentinvention are especially suitable for use in crop protection forcontrolling unwanted plant growth both on uncultivated land and in cropstolerant to the herbicide(s) of constituent (a) used in the context ofthe present invention.

In a further aspect, the present invention relates to a method ofcontrolling unwanted plant growth, which comprises applying an effectiveamount of a combination according to the present invention as definedherein to plants, parts of plants or the cultivation area.

In a further aspect, the present invention relates to the use of acombination according to the present invention as defined herein forcontrolling unwanted plant growth.

EXAMPLES

Unless indicated otherwise, all amounts indicated in the following arein percent by weight (wt.-%).

Abbreviations and products used (including trade names):

a.i.=(Amount of) Active ingredient

GFA=Glufosinate-ammonium

GIPA=Glyphosate-isopropylammonium

®Genapol LRO Paste=C₁₂/C₁₄ fatty alcohol diethylene glycol ether sulfatesodium, used as a 70% wt.-% solution in water, Clariant)

®Salacos 99=Isononyl isononanoate (Nisshin Oillio)

POVAL™ 4-88=Polyvinyl alcohol (degree of hydrolysis of the polyvinylacetate about 88%) (Kuraray)

®Disflamoll TOF=Tri-(2-ethylhexyl)-phosphate (Lanxess)

DowanoP PM=Propylene glycol mono methyl ether (Dow)

®Silcolapse 482=Polydimethylsiloxane defoamer with silica gel (BluestarSilicones)

®Agnique PG 8105=C₈-C₁₀ Alkyl polyglycosides (used as 62-65 wt.-%strength aqueous solution (BASF)

®Reax 88A=Lignosulfonic acid, sodium salt, sulfomethylated (sodium saltof a chemically modified low molecular weight Kraft lignin polymersolubilized by five sulfonate groups, DKSH)

®Ultrazine NA=Purified sodium lignosulphonate (Borregaard)

Synergen™ GA=C₈-C₁₀ alkylglucamides (used as a 50% strength aqueoussolution, Clariant)

®Sokolan CP5=Copolymer of methacrylic acid and acrylic acid (used as a40% strength aqueous solution, BASF)

®Ammonyx M=Myristamine Oxide (used as a 25% strength aqueous solution,Stepan)

TABLE R1 Reference formulation GFA SL196 Amount Constituent in wt.-%Glufosinate-ammonium (GFA) 18 Genapol LRO Paste 22.51-Methoxy-propan-2-ol 10 Silcolapse 482 0.25 Water ad 100

TABLE R2 Reference formulation GIPA51 Amount Constituent in wt.-%Glyphosate-isopropylammonium (GIPA) 51 3-Isotridecyloxypropanamine,ethoxylated (5 EO) 7.5 Water 41.5

BIOLOGICAL EXAMPLES

The growth stages of the different weed species are indicated accordingto the BBCH monograph “Growth stages of mono- and dicotyledonousplants”, 2nd edition, 2001, ed. Uwe Meier, Federal Biological ResearchCentre for Agriculture and Forestry (Biologische Bundesanstalt für Landand Forstwirtschaft). The respective BBCH stages are indicated for thedifferent weed species hereinafter.

In the following Tables 01 to 07, for reasons of comparability of thetest results, the amounts in percent indicated for the respective testcompounds are by weight and refer to the absolute amount of therespective test compound used, i.e. any diluents (like e.g. water)present in the commercial product with the trade names indicated aboveare not reflected in said amounts. For example, if Ammonyx M (a 25%strength aqueous solution of Myristamine Oxide) was used, an amount of3% indicated in a Table is the amount of Myristamine Oxide (andcorresponds to an amount of 12% of the commercial product Ammonyx M).

Greenhouse rainfastness trials: Chenopodium album (CHEAL) and Loliummultiflorum (LOLMU) plants were grown in 7 cm pots in the greenhouseuntil they reached an adequate developmental stage, provided in thedifferent results tables and applied after selection for uniform plants.400 g a.i./ha GFA SL196 formulation and mixtures with different testcompounds and the GFA SL196 formulation in a rate of 400 g a.i./ha and10 wt.-% of test compounds were applied in a linear track sprayeroutfitted with 002 flat fan nozzles at a water application rate of 300L/ha. Six sets of plants containing 4 replications of each of the weedspecies were treated with the different test mixtures and the referencecontaining the GFA SL196 formulation. The first set did not receiveirrigation after treatment, whereas the 5 remaining sets received anirrigation of 5.5 L/m² at 2 h after the initial herbicide treatment. Theirrigation was applied on a linear track sprayer outfitted with 8005flat fan spray nozzles in a row at 1.5 Bar water pressure providing 5.5mm of rain for each set of plants. Fourteen days after application (14DAA) the different weed species were visually rated on a percentagescale in relation to the untreated control (100%=all plants dead;50%=green plant biomass reduced by 50%, and 0%=no discernibledifference=like control plot) (see Table 01 and Table 02 for Chenopodiumalba).

In the second rainfastness trial the conditions were similar withexception that the application rate of GFA was reduced to 350 g a.i./haGFA. The concentration of selected test compounds was reduced to 3 wt.-%and 5 wt.-%, respectively (Table 03 Chenopodium alba).

In a further rainfastness trial, glyphosate (used as 540 g a.i./ha GIPA)was tested in mixture with POVAL 4-88 in an amount of 5 wt.-% (Table 04Chenopodium alba).

TABLE 01 Comparative tests with Glufosinate-ammonium (addition of 10wt.-% of the respective test compound to 400 g a.i./ha GFA) onChenopodium alba plants (BBCH18-20) in greenhouse rain assay CHEAL (BBCH18-20) % control compared to untreated plants Composition No Simulatedrain of % reduction of Tank mix 400 g a.i./ha GFA (SL196) simulated 5.5L/m² 2 h after control due to [+10 wt.-% of test compound] rainapplication simulated rain GFA SL196 (Reference) 100 29 −71 GFA SL196 +10% Reax 88 100 13 −87 GFA SL196 + 10% Ultrazine NA 100 14 −86 GFASL196 + 10% Synergen GA 100 14 −86 GFA SL196 + 10% Sokolan CP5 100 30−70 GFA SL196 + 10% Ammonyx M 100 26 −74

TABLE 02 Test results with compositions according to the invention withGlufosinate-ammonium (addition of 10 wt.-% of POVAL 4-88 to 400 ga.i./ha GFA SL196) on Chenopodium alba plants (BBCH 18-20) in greenhouserain assay CHEAL (BBCH 18-20) % control compared to untreated plantsSimulated rain % reduction Composition No of 5.5 L/m² 2 of control dueTank mix 400 g a.i./ha GFA (SL196) simulated h after to simulated [+10%of test compound] rain application rain GFA SL196 (Reference) 100 29 −71GFA SL196 + 10% POVAL 4-88 100 66 −34

TABLE 03 Test results with compositions according to the invention withGFA (addition of 5 wt.-% POVAL 4-88 and 3 wt.-% Salacos 99 or DisflamollTOF to 350 g a.i./ha GFA SL196) on Chenopodium alba plants (BBCH 17-19)in greenhouse rain assay CHEAL (BBCH 17-19) % control compared tountreated plants Simulated rain % reduction Composition No of 5.5 L/m² 2of control due Tank mix 350 g a.i./ha GFA (SL196) simulated h after tosimulated [+ test compound(s)] rain application rain GFA SEI96(Reference) 90 19 −79 GFA SL196 + 5% POVAE 4-88 + 3% 99 38 −62 Salacos99 GFA SL196 + 5% POVAL 4-88 + 3% 89 34 −62 Disflamoll TOF

TABLE 04 Test results with compositions according to the invention withGlyphosate (with addition of 5 wt.-% POVAL 4-88 to 540 g a.i./ha GIPA)on Chenopodium alba (CHEAL) plants (BBCH 17-19) in greenhouse rain assayCHEAL (BBCH 17-19) % control compared to untreated plants CompositionSimulated rain % reduction Tank mix 540 g a.i./ha GIPA No of 5.5 L/m² 2of control due (Applied at 300 L/ha) simulated h after to simulated [+test compound(s)] rain application rain GIPA51 (Reference) 35 8 −77GIPA51 + 5% POVAL 4-88 42 29 −31

Field Trial to Evaluate Weed Control Efficacy:

Compounds that were tested in the greenhouse before, were tested in thefield, with 350 g a.i./ha of GFA, alone as well as in variouscombinations to evaluate efficacy under field conditions. Applicationswere made to seeded weeds in a replicated randomized complete blockdesign. Test compounds were added to the GFA SL196 formulation at a rateof 3% wt.-% and 5% wt.-%, respectively. The plots were sprayed using a140 L/ha application volume with a hand held spray boom. Fourteen daysafter application (14 DAA) the different weed species were visuallyrated on a percentage scale in relation to the untreated control(100%=all plants dead; 50%=green plant biomass reduced by 50%, and 0%=nodiscernible difference=like control plot) (see Table 05a, Table 05b,Table 06).

The effects on the following weeds were assessed (depending on presencein the respective field): Abutilon theophrasti (ABUTH), Chenopodiumalbum (CHEAL), Avena fatua (AVEFA), Bassia scoparia (KCHSC) and Triticumaestivum (TRZAS).

TABLE 05a Weed control efficacy for dicotyledonous weeds - Field trialsfor compositions with Glufosinate-ammonium improving activity in fieldtrials. Trials performed in tank mix of 350 g a.i. GFA SL196 +Disflamoll TOF; Salacos 99; POVAL 4-88; BBCH code provided at time ofapplication % Control compared to untreated plants Tank mix 350 ga.i./ha GFA (SL196) ABUTH CHEAL CHEAL KCHSC [+ test compound(s)] BBCH 14BBCH 18 BBCH 18 BBCH 20 GFA SL196 (Reference) 74 75 39 88 GFA SL196 + 3%Salacos 99 (*) 79 82 42 89 GFA SL196 + 3% Disflamoll TOF (*) 80 72 40 92GFA SL196 + 5% POVAL 4-88 + 3% 52 93 Salacos 99 GFA SL196 + 5% POVAL4-88 + 3% 43 94 Disflamoll TOF (*): Not a combination according to theinvention

TABLE 05b Weed control efficacy for monocotyledonous weeds (grasses) -Field trials for compositions according to the invention withGlufosinate-ammonium improving activity in field trials. Trialsperformed in tank mix of 350 g a.i. GFA + Disflamoll TOF; Salacos 99;POVAL 4-88; BBCH code provided at time of application % Control comparedto untreated plants Tank mix 350 g a.i./ha GFA (SL196) AVEFA AVEFA [+test compound(s)] BBCH 23 BBCH 22 GFA SL196 (Reference) 32 75 GFASL196 + 3% Salacos 99 (*) 40 79 GFA SL196 + 3% Disflamoll TOF (*) 37 82GFA SL196 + 5% POVAL 4-88 + 3% 40 85 Salacos 99 GFA SL196 + 5% POVAL4-88 + 3% 40 83 Disflamoll TOF (*): Not a combination according to theinvention

TABLE 06 Weed control efficacy - Comparative field trial results forformulations with Glufosinate-ammonium. Trials performed in tank mix of350 g a.i. GFA + 3 wt.-% test compound, respectively; BBCH code providedat time of application % Control compared to untreated plants Tank mix350 g a.i./ha GFA (SL196) AVEFA KCHSC CHEAL [+3 wt.-% test compound]BBCH 23 BBCH 20 BBCH 18 GFA SL196 (Reference) 44 60 66 GFA SL196 + 3%Reax 88A 20 33 30 GFA SL196 + 3% Synergen GA 25 53 47 GFA SL196 + 3%Ammonyx M 22 20 28 GFA SL196 + 3% Sokolan CP5 30 50

Field Trial to Determine Rainfastness:

350 g a.i./ha GFA as GFA 196SL formulation alone and in combination with5 wt.-% POVAL 4-88 were applied to wheat (TRZAS) plants at growth stageBBCH 23. The plots were sprayed with an application volume of 140 L/hawith a hand held spray boom. Approximately 20 L/m² of water wasirrigated 1 h after application on half the treatments. Fourteen daysafter application (14 DAA) the different weed species were visuallyrated on a percentage scale in relation to the untreated control(100%=all plants dead; 50%=green plant biomass reduced by 50%, and 0%=nodiscernible difference=like control plot) (see Table 7).

TABLE 7 Field trials to determine rainfastness of compositions accordingto the invention in wheat (TRZAS). Trials were performed with tank mixesof 350 g a.i. GFA + 5 wt.-% POVAL 4-88; BBCH code provided at time ofapplication TRZAS (BBCH 23) % control compared to untreated plantsSimulated rain % reduction Tank mix field trial No of 20 L/m² 2 ofcontrol due (Applied at 187 L/ha) 350 g a.i. simulated h after tosimulated [+ test compound(s)] rain application rain GFA SL196(Reference) 28 0 −100 GFA SL196 + 5% POVAL 4-88 48 29 −40

In the following preferred embodiments of constituent (II) used incombinations according to the present invention are described.

Embodiment 1: Constituent (II) used in a combination according to thepresent invention preferably is a composition comprising or consistingof

(a) one or more water-soluble herbicidal active crop protectantingredients (type (a) active ingredients),

(b) one or more C₆-C₁₆ fatty alcohol polyethylene glycol ether sulfatesand/or C₆-C₁₆ alkylpolyglycosides, and/or C₁₀-C₁₈ fatty alkyl amineethoxylates, and optionally one or more further constituents selectedfrom the group consisting of constituents (d) to (h):

(d) organic solvents,

(e) water,

(f) other surfactants (i.e. different from constituent (b),

(g) other formulation adjuvants (i.e. different from constituents (b) to(f)),

(h) one or more other herbicidal active crop protectant ingredientsand/or herbicide safeners.

Embodiment 2 is a composition according to Embodiment 1, comprising

constituent (a) in a total amount 5% to 70% by weight,

constituent (b) in a total amount 5% to 60% by weight,

and optionally one or more further constituents selected from the groupconsisting of constituents (d) to (h)

constituent (d) in a total amount 0% to 15% by weight,

constituent (e) in a total amount 0.1% to 60% by weight,

constituent (f) in a total amount 0.1% to 30% by weight,

constituent (g) in a total amount 0.1% to 20% by weight,

constituent (h) in a total amount 0.1% to 20% by weight,

in each case based on the total weight of the composition.

Embodiment 3 is a composition according to Embodiment 1 or Embodiment 2,comprising

constituent (a) in a total amount 10% to 60% by weight,

constituent (b) in a total amount 5% to 50% by weight,

constituent (e) in a total amount 20% to 60% by weight,

and optionally one or more further constituents selected from the groupconsisting of constituents (d), (f), (g) and (h)

constituent (d) in a total amount 0% to 15% by weight,

constituent (f) in a total amount 0.1% to 20% by weight,

constituent (g) in a total amount 0.1% to 12% by weight,

constituent (h) in a total amount 0.1% to 12% by weight,

in each case based on the total weight of the composition.

Embodiment 4 is a composition according to any one of Embodiments 1 to3, comprising as constituent (a) one or more active ingredients selectedfrom the group consisting of glufosinate and salts thereof, glyphosateand salts thereof, MCPA and salts thereof, dicamba and salts thereof,2,4-D and salts thereof and dichlorprop and the salts thereof.

Embodiment 5 is a composition according to any one of Embodiments 1 to4, wherein constituent (a) comprises or consists of one or more activeingredients selected from the group consisting of glufosinate-ammonium,glufosinate-sodium, L-glufosinate-ammonium, L-glufosinate-sodiumglyphosate-potassium, glyphosate-ammonium, glyphosate-dimethylammonium,glyphosate-isopropylammonium, glyphosate-trimesium (sulfosate),dicamba-diglycolamine, dicamba-BAPMA and 2,4-D-choline.

Embodiment 6 is a composition according to any one of Embodiments 1 to5, wherein constituent (b) comprises or consists of one or more C₁₀-C₁₆fatty alcohol diethylene glycol ether sulfate salts and/or C₈-C₁₂alkylpolyglucosides with a degree of polymerization of less than 5,and/or C₁₂-C₁₆ alkyl amine ethoxylates with 2 to 10 ethylene oxide (EO)units.

Embodiment 7 is a composition according to any one of Embodiments 1 to6, wherein constituent (b) comprises or consists of one or more C₁₂-C₁₄fatty alcohol diethylene glycol ether sulfate sodium-, potassium-,ammonium-salts and/or C₈-C₁₀ alkylpolyglucosides with a degree ofpolymerization of less than 2, and/or C₁₂-C₁₄ alkyl amine ethoxylateswith 4 to 8 ethylene oxide (EO) units.

Embodiment 8 is a composition according to any one of Embodiments 1 to7, additionally comprising constituent (c), wherein constituent (c)comprises or consists of one or more esters selected from the groupconsisting of (c1) to (c3):

(c) one or more esters selected from the group consisting of (c1) to(c3):

(c1) R¹COOR², wherein R¹ denotes a C₅-C₁₃ alkyl group and R² denotes aC₆-C₁₄ alkyl group, wherein the total number of carbon atoms in R¹ andR² taken together is an integer in the range of from 14 to 22,

(c2) R³OOC—(CH₂)x-COOR⁴, wherein R³ and R⁴, independent of each other,denote a C₄-C₁₂ alkyl group, and x is an integer in the range of from 1to 6,

(c3) (R⁵O)₃P═O, wherein R⁵, independent of each other, denote a C₄-C₁₆alkyl group, wherein the total number of carbon atoms in the three R⁵taken together is an integer in the range of from 18 to 42.

Embodiment 9 is a composition according to Embodiment 8, whereinconstituent (c) comprises or consists of one or more esters selectedfrom the group consisting of (c1) to (c3):

(c1) R¹COOR², wherein R¹ denotes a C₇-C₉ alkyl group and R² denotes aC₈-C₁₀ alkyl group, wherein the total number of carbon atoms in R¹ andR² taken together is an integer in the range of from 16 to 20,

(c2) R³OOC—(CH₂)x-COOR⁴, wherein R³ and R⁴, independent of each other,denote a C₆-C₁₀ alkyl group, and x is an integer in the range of from 2to 5,

(c3) (R⁵O)₃P═O, wherein R⁵, independent of each other, denote a C₆-C₁₂alkyl group.

Embodiment 10 is a composition according to any one of Embodiments 1 to9, wherein the total amount of constituent (a) to the total amount ofconstituent (c) is in the range of from 125:1 to 1:1, preferably in therange of from 100:1 to 3:2, in each case based on the total weight ofthe composition.

Embodiment 11 is a composition according to any one of Embodiments 8 to10, wherein the composition comprises constituent (c) in a total amountof 0.5% to 12% by weight, preferably in a total amount of 1% to 10% byweight, in each case based on the total weight of the composition.

Embodiment 12 is a composition according to any one of Embodiments 1 to11, wherein the ratio by weight of the total amount of constituent (a)to the total amount of constituent (b) is in the range of from 10:1 to1:6, and preferably is in the range of from 8:1 to 1:3, in each casebased on the total weight of the composition.

Embodiment 13 is a composition according to any one of Embodiments 8 to12, wherein the ratio by weight of the total amount of constituent (a)to the total amount of constituent (c) is in the range of from 60:1 to2:1, preferably is in the range of from 40:1 to 3:1, in each case basedon the total weight of the composition.

Embodiment 14 is a composition according to any one of Embodiments 1 to13, wherein constituent (d) comprises or consists of propylene glycolmonomethyl ether, dipropylene glycol and/or propylene glycol, andpreferably comprises 1-methoxy-2-propanol,

and/or

constituent (f) comprises or consists of alkyl sulfosuccinate salts,preferably comprises or consists of C₆-C₁₄ alkyl sulfosuccinatemonoester salts, more preferably comprises or consists of laureth-3sulfosuccinate salts, in particular disodium laureth-3 sulfosuccinate,

and/or

constituent (g) comprises a defoaming agent, preferably anpolydimethylsiloxane oil with silica gel.

What is claimed is:
 1. A combination comprising constituents (I) and II:(I) one or more polyvinyl alcohols; and (II) a composition comprisingconstituents (a) and (b): (a) one or more water-soluble herbicidalactive crop protectant ingredients; and (b) one or more C₆-C₁₆ fattyalcohol polyethylene glycol ether sulfates and/or C₆-C₁₆alkylpolyglycosides, and/or C₁₀-C₁₈ fatty alkyl amine ethoxylates;wherein a ratio of a total amount of constituent (I) to a total amountof constituent (II) is in a range of from 1:100 to 1:5, based on a totalweight of the combination.
 2. The combination as claimed in claim 1,wherein the total amount of the constituent (I) to the total amount ofthe constituent (II) is in the range of from 1:50 to 1:10, based on thetotal weight of the combination.
 3. The combination as claimed in claim1, wherein the total amount of the constituent (I) to the total amountof the constituent (II) is in the range of from 1:30 to 1:12, based onthe total weight of the combination.
 4. The combination as claimed inclaim 1, wherein said combination is in a form of a kit-of-parts, aco-pack or a tank-mix.
 5. The combination as claimed in claim 1, whereinthe constituent (I) comprises polyvinyl alcohols with a degree ofpolymerization in a range of 150 to
 1000. 6. The combination as claimedin claim 1, wherein the constituent (a) of the constituent (II)comprises one or more water-soluble herbicidal active crop protectantingredients selected from the group consisting of glufosinate and saltsthereof, glyphosate and salts thereof, MCPA and salts thereof, dicambaand salts thereof, 2,4-D and salts thereof, and dichlorprop and thesalts thereof.
 7. The combination as claimed in claim 1, wherein theconstituent (b) of the constituent (II) comprises one or more C₁₀-C₁₆fatty alcohol diethylene glycol ether sulfate salts and/or C₈-C₁₂alkylpolyglucosides with a degree of polymerization of less than 5,and/or C₁₂-C₁₆ alkyl amine ethoxylates with 2 to 10 ethylene oxide (EO)units.
 8. The combination as claimed in claim 1, wherein the combinationor the constituent (II) comprises one or more further constituentsselected from a group consisting of constituents (c) to (h): (c) one ormore esters selected from the group consisting of (c1) to (c3): (c1)R¹COOR², wherein R¹ denotes a C₅-C₁₃ alkyl group and R² denotes a C₆-C₁₄alkyl group, wherein a total number of carbon atoms in R¹ and R² takentogether is an integer in a range of from 14 to 22; (c2)R³OOC—(CH₂)x-COOR⁴, wherein R³ and R⁴, independent of each other, denotea C₄-C₁₂ alkyl group, and x is an integer in a range of from 1 to 6; and(c3) (R⁵O)₃P═O, wherein R⁵, independent of each other, denote a C₄-C₁₆alkyl group, wherein a total number of carbon atoms in the three R⁵taken together is an integer in a range of from 18 to 42; (d) organicsolvents; (e) water; (f) other surfactants; (g) other formulationadjuvants; and (h) one or more other herbicidal active crop protectantingredients and/or herbicide safeners.
 9. The combination as claimed inclaim 1, wherein in the constituent (II) a ratio by weight of a totalamount of the constituent (a) to a total amount of the constituent (b)is in a range of from 10:1 to 1:6.
 10. The combination as claimed inclaim 1, wherein a constituent (c) is present, wherein the constituent(c) comprises one or more esters selected from the group consisting of(c1) to (c3): (c1) R¹COOR², wherein R¹ denotes a C₇-C₉ alkyl group andR² denotes a C₈-C₁₀ alkyl group, wherein a total number of carbon atomsin R¹ and R² taken together is an integer in a range of from 16 to 20;(c2) R³OOC—(CH₂)x-COOR⁴, wherein R³ and R⁴, independent of each other,denote a C₆-C₁₀ alkyl group, and x is an integer in a range of from 2 to5; and (c3) (R⁵O)₃P═O, wherein R⁵, independent of each other, denote aC₆-C₁₂ alkyl group.
 11. The combination as claimed in claim 8, whereinthe constituent (c) is present, and a ratio by weight of a total amountof the constituent (a) to a total amount of the constituent (c) is in arange of from 60:1 to 2:1 based on a total weight of the combination.12. The combination as claimed in claim 8, wherein a ratio of a totalamount by weight of polyvinyl alcohols of the constituent (I) to a totalamount of the constituent (c) is in a range of from 5:1 to 1:5, based ona total weight of the combination.
 13. The combination as claimed inclaim 1, wherein the combination is a tank-mix obtainable or obtained bymixing the combination as defined in claim 1 and water as a constituent(III), wherein a ratio by weight of a total amount of the constituent(III) to a total amount of the said combination in the tank-mix is in arange of from 1000:1 to 10:1.
 14. A method of controlling unwanted plantgrowth, which comprises applying an effective amount of a combination asdefined in claim 1 to a plant, a part of a plant, or a cultivation area.15. (canceled)
 16. The combination as claimed in claim 1, wherein theconstituent (I) comprises polyvinyl alcohols with a degree ofpolymerization in a range of 250 to
 750. 17. The combination as claimedin claim 1, wherein in the constituent (II) a ratio by weight of a totalamount of the constituent (a) to a total amount of the constituent (b)is in a range of from 8:1 to 1:3.
 18. The combination as claimed inclaim 8, wherein the constituent (c) is present, and a ratio by weightof a total amount of the constituent (a) to a total amount of theconstituent (c) is in a range of from 40:1 to 3:1, based on a totalweight of the combination.
 19. The combination as claimed in claim 8,wherein a ratio of a total amount by weight of polyvinyl alcohols of theconstituent (I) to a total amount of the constituent (c) is in a rangeof from 3:1 to 1:3, based on a total weight of the combination.
 20. Thecombination as claimed in claim 1, wherein the combination is a tank-mixobtainable or obtained by mixing the combination as defined in claim 1and water as a constituent (III), wherein a ratio by weight of a totalamount of the constituent (III) to a total amount of the saidcombination in the tank-mix is in a range of from 500:1 to 25:1.